Condensation products of benzanthrone-bz-carboxylic acid chloride and fluoranthene



Patented June 10, 1952 puns-o STAT-ES PATENT OFFICE CONDENSATIO-N-PRODUCTS OF BENZAN- 'iTHRONE-Bm-GARBOXYLI-C ACID CHLO- RIDE ANDFLUOR-ANTHENE Wilhelmi Schmidt-Nickels, Little York, N. J assignoratoGeneral Aniline & Film Corporation, New York, N. Y., a corporation ofDelaware No Drawing. Application February 19, 1949, Serial No. 77,438

4 Claims. (01. 260-362) said-compound being unsubstitutedor containingone or more nuclear substituents-of the class consisting of halogen,-alkyl, .alkoxy acylamino, nitro and sulfo groups.

The dyestufis of this invention are prepared by reacting'equal'molarproportions of fluora-nthene and benzanthrone Bzi-carboxylic acid.chloride together with anhydrous aluminum chloride in a solvent such asnitrobenzene. The resultant compound is then ring-closed by alkalifusion as with potassium hydroxide in alcohol. Since some of the productof this latter reaction may be in the leuco form, oxygen is passedthrough the material to convert all of the product to the dyestuffhaving the general formula indicated above. The first reaction iscarried out at a temperature in the range 60 to 100 C. and preferably inthe range '75 to 80 C. The alkali fusion may be accomplished at atemperature of about 200 to 250 C. and'-preferably about 230 C. The timeof the first reaction is several hours while the alkali fusion takes:only a few minutes. The dyestufis'obtained, dye "cotton and othercellulose (fibers a chocolate brown in the usual vat dye {process itoshades having excellent fastness to chlorinebleach.

A preferred method of preparing the dyestuffs of my invention isillustrated by the following example, wherein parts are by weight,buta'itwill be understood -that the invention: is not 'limitedtheretotand that variations:and substitutionsrmay be made within'. thescope of the appended claims.

Example A charge. of '2I0, parts nitrobenzene, 11-.7 partsbenzanthrone-Bzi-carboxylic 'acidchloride, 18.0 parts'anhydrousaluminumchlori-de; and:8;l: pa'rts .fluoranthene is stirred at"l5=80 C.for .3 -hours. The reaction product ispouredintoa little watercontaining '24 parts hydrochloric acid conce'n- .trated (35%). Thenitrobenzene -is--then.-re-

moved 'by". steam distillation. :The solidreaction product isfilteredand forremoval'ofipossibly present benzanthrone-Bzi carboxylic :-acidextracted eat-70 C. with a mixture of 108 parts of concentrated ammonia(28%) and "600 .parts water. After filtrationand-washing to neutralitythe pro duct-weighed 18.1, parts. The cyclization :of. thethusiobtainedketone is carried out as fol lows:

A charge of 24 parts by weight alcohol -andv :parts potassium hydroxideis heated under agitation to 230 C. while alcohol is allowedto :distilloff. At 230 C. 5 parts of the ketone is introduced into the melt. Afterstirring at 230 C. for 5 minutes the, mass is poured into 500 parts byweight water. A portion of the formed dyestuff is present in its leucoform which is soluble in the alkaline water givin a violet color. Toprecipitate all the dyestuff air is blown through the solution for /2hour. The dyestuff is filtered, washed neutral and dried. A dyestufipaste can be made by the known method of dissolving the dyestuff inconcentrated sulfuric acid and pouring the solution in water. Theproduct dyes cotton from a hydrosulfite vat a pleasant chocolate 3 brownshade of excellent chlorine fastness. This reaction may be representedby the following scheme:

Nitrobenzene H O m 0 E KOH Alcohol Similar dyestufis are obtained byemploying, instead of fluoranthene and benzanthrone B21- carboxylic acidchloride in theforegoing example, equivalent quantities of nuclearsubstitution products of either one or both of these intermediatescontaining one or more alkyl groups apiece. Alternatively, the compoundobtained by the example, either unsubstituted or containing alkylsubstituents may have other substituents introduced by the knownprocedures such as halogen, alkoxy, nitro, sulfo and acylamino groups.Substituent alkyl groups in the original intermediates, of course, maynot be present in positions to block the reaction and ring closure (4,in the benzanthrone and 11, 12 in the fiuoranthene). It will beunderstood that such groups as halogen groups present in the originalintermediates might not withstand the drastic conditions of thereactions and if these substituents are desired, they may be introducedafter the dyestuff has been formed by procedures customarily used forintroducing such substituents into vat dyestuffs of the benzanthroneseries.

If desired, chocolate brown vat dyestuffs of this invention can beconverted into the alkali metal salt of the sulphuric acid ester of thecorresponding leuco compound by the usual methods, for example, byreduction of the dyestuffs with a hydrogen liberating metal such as ironor zinc, preferably accompanied by a minor amount of copper, in amixture of chlorsulfonic acid and pyridine followed by drowning of thereaction mixture in an aqeous alkali metal carbonate solution andsalting out of the resulting leuco ester salt after removal of thepyridine by distillation. The resulting leuco sulphuric acid ester saltsyield shades having color and fastness properties simi lar to thoseobtained by vat dyeing processes from the original dyestuifs, uponapplication by printing or dyeing of the material and development of thecolor by treatment with an acid oxidizing bath.

Iclaim:

1. A compound having the following formula:

W i a 2. A vat dyestufi having the following formula:

3. An alkali metal salt of the sulphuric acid ester of the leucocompound of the dyestuif defined in claim 2.

4. A process for preparing a chocolate brown vat dyestuff of thebenzanthrone series which comprises reacting one mole ofbenzanthrone-Bzicarboxylic acid chloride with one mole of fluorantheneat an elevated temperature and subsequently ring closing the ketone thusformed.

WILHELM SCHMIDT-NICKELS.

REFERENCES CITED The following references are of record in the file ofthis patent:

FOREIGN PATENTS Number Country Date 123,267 Switzerland May 4, 1926

4. A PROCESS FOR PREPARING A CHOCOLATE BROWN VAT DYESTUFF OF THEBENZANTHRONE SERIES WHICH COMPRISES REACTING ON MOLE OFBENZANTHRONE-BZ1CARBOXYLIC ACID CHLORIDE WITH ONE MOLE OF FLUORANTHENEAT AN ELEVATED TEMPERATURE AND SUBSEQUENTLY RING CLOSING THE KETONE THUSFORMED.